CN104646066B - A kind of preparation method of polymer/titanium dioxide multiple elements design photocatalysis film - Google Patents

A kind of preparation method of polymer/titanium dioxide multiple elements design photocatalysis film Download PDF

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CN104646066B
CN104646066B CN201310598159.3A CN201310598159A CN104646066B CN 104646066 B CN104646066 B CN 104646066B CN 201310598159 A CN201310598159 A CN 201310598159A CN 104646066 B CN104646066 B CN 104646066B
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titanium dioxide
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CN104646066A (en
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孟祥福
刘秀云
吕立贞
王丽丽
刘彦鹏
陈啟荣
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Capital Normal University
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Abstract

The present invention relates to the preparation method of a kind of polymer/titanium dioxide multiple elements design photocatalysis film.The present invention is titanate esters to be hydrolyzed in organic acid soln, is dried to obtain soluble titanium dioxide solid dry gel;Aqueous solution after solid dry gel is dissolved in water and containing water-soluble polymer, add silver nitrate aqueous solution, after being placed under uviol lamp irradiation, add graphene oxide water solution, it is placed in reactor and carries out hydrothermal treatment consists, then film, the high transparency thin film obtained, again through high-temperature vacuum heat treatment, i.e. can get high transparency polymer/titanium dioxide multiple elements design photocatalysis film.Polymer/titanium dioxide multiple elements design the photocatalysis film using the preparation method of the present invention to obtain has the advantages such as transparency height, good mechanical properties, there is good photocatalytic activity under visible light illumination, can be used for the photocatalytic degradation of Organic Pollutants in Wastewater, and can recycle.The preparation method of the present invention is simple, device therefor processing ease.

Description

A kind of preparation method of polymer/titanium dioxide multiple elements design photocatalysis film
Technical field
The present invention relates to the preparation method of a kind of polymer/titanium dioxide multiple elements design photocatalysis film.
Background technology
The ring caused by organic pollution (such as halides, two English, pesticide, dyestuff etc.) of poisonous difficult degradation Border problem has become 21 century affects human survival and healthy significant problem.It is difficult to process by prior art These pollutant, therefore studying the new effective method controlling poisonous persistent organic pollutants becomes The key subjects the most extremely paid close attention to.At present, organic pollution for poisonous difficult degradation enters in the world Row degradation treatment have most application prospect, to study most active technology be under the effect of photocatalyst, with Inexpensively, clean and endless solar energy is the energy, with the oxygen in air and other " green " Oxidative species is (such as H2O2Deng) it is the technology of catalytic oxidization degradation of oxidant, this technology finally can be by Organic pollution is completely decomposed into CO2、H2O and other inorganic salt, and there is no secondary pollution.
Titanium dioxide optical catalyst powder body forms suspension system, later stage with treatment sewage in actual applications Process has to pass through the method such as filtration, centrifugal, flocculation and is isolated recovery, and process is complicated, adds back Receiving difficulty, cyclic utilization rate is low.In order to solve nano-TiO2What powder body reclaimed in actual application asks Topic, people are often loaded on host material, such as glass, silica gel, zeolite, rustless steel etc., But nano-TiO2Load on host material, frequently can lead to specific surface area reduce, with organic pollution materials The probability of contact reduces, and has had a strong impact on light-catalyzed reaction speed.Therefore, nano-TiO2Load not only The recovery problem of suspension system to be considered, and to keep nano-TiO after load2Effectively photocatalytic activity point Quantity.The present invention uses high transparency thin polymer film to be that carrier is prepared composite photo-catalyst and not only can be improved The utilization ratio of light, but also recycling efficiency can be greatly improved, easy to operate, dioxy therein Change titanium, graphene oxide and Ag composition multicomponent system and can be effectively improved photocatalytic activity, add poly-simultaneously The mechanical property of compound self, the visible light responsive photocatalyst for exploitation efficient stable provides new think of Road.
Summary of the invention
It is an object of the invention to provide that a kind of reaction condition is gentle, equipment needed thereby is simple, raw material is easy to get, suitable Preparation method for the polymer/titanium dioxide multiple elements design photocatalysis film of large-scale production.
The preparation method is that and titanate esters is hydrolyzed in organic acid soln, be dried to obtain solvable Property titanium dioxide solids xerogel;After soluble titanium dioxide solid dry gel is dissolved in water and containing water solublity The aqueous solution of polymer, adds silver nitrate aqueous solution, after ultraviolet light irradiates, adds graphite oxide Aqueous solution, is placed in reactor and carries out hydrothermal treatment consists, then film, the high transparency thin film warp again obtained High-temperature vacuum heat treatment, i.e. can get high transparency polymer/titanium dioxide multiple elements design photocatalysis film.Adopt Polymer/titanium dioxide multiple elements design the photocatalysis film obtained by the preparation method of the present invention has transparency The advantages such as height, favorable dispersibility, have good photocatalytic activity under visible light illumination, can be used for giving up The photocatalytic degradation of organic pollutants, and can recycle.Polymer/the titanium dioxide of the present invention The preparation method of titanium multiple elements design photocatalysis film is simple, device therefor processing ease.
The preparation method of the polymer of the present invention/titanium dioxide multiple elements design photocatalysis film includes following step Rapid:
(1) titanate esters is joined in organic acid soln it is hydrolyzed, wherein: titanate esters: rubbing of organic acid That ratio is 1:0.5~10;(mixing time be generally 1~3 hour) is stirred at room temperature, obtains brown solution, The brown solution obtained directly is dried in air at room temperature, removes volatile by-product, To titanium dioxide xerogel;
(2) titanium dioxide xerogel and water-soluble polymer step (1) obtained is dissolved in water also Silver nitrate aqueous solution is added, wherein: titanium dioxide xerogel: water-soluble polymer: silver nitrate after merging Mass ratio be 1:(0.5~10): (0.001~0.01);After mix homogeneously, it is placed under uviol lamp irradiation 0.5~3 After hour, adding graphene oxide water solution, wherein graphene oxide is 1 with the mass ratio of titanium dioxide: 10~500;It is subsequently placed in autoclave and carries out hydrothermal treatment consists, obtain after hydrothermal treatment cooling Solution on solid substrate, carry out film, drying at room temperature obtains high transparency thin film;
(3) the high transparency thin film that step (2) obtains is carried out high-temperature heat treatment under vacuum, the most available High transparency polymer/titanium dioxide/graphene oxide/silver multiple elements design photocatalysis film.
Polymer/titanium dioxide/graphene oxide/silver multiple elements design photocatalysis film that the present invention obtains has Favorable dispersibility, the feature (such as embodiment 1) that light transmittance is high.
Heretofore described titanate esters is selected from tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate In one or more.
The mass concentration of heretofore described organic acid soln is 1%~99%.Described organic acid is preferred One in acetic acid, trifluoroacetic acid, trichloroacetic acid.
Heretofore described water-soluble polymer is preferably selected from polyvinyl alcohol, polyacrylic acid, polyethylene pyrrole One in pyrrolidone.
The concentration of heretofore described silver nitrate aqueous solution is 0.1~1mol/L.
The concentration of heretofore described graphene oxide water solution is 0.1~1g/mL.
The temperature of heretofore described hydrothermal treatment consists is preferably 90~180 DEG C;The time of hydrothermal treatment consists is preferred It it is 0.5~10 hour.
The heretofore described temperature carrying out high-temperature heat treatment under vacuum is 180~200 DEG C;High temperature The time of heat treatment is preferably 0.5~5 hour.Result shows that the time of (table 1) high-temperature heat treatment is 0.5~5 Hour the transparency of product best.
The preparation method of the polymer of the present invention/titanium dioxide multiple elements design photocatalysis film has following excellent Point:
(1) preparation condition is gentle, and energy consumption is little, and low cost is suitable to large-scale production.
(2) resulting polymers/titanium dioxide multiple elements design photocatalysis film have simultaneously higher ultraviolet light and Visible light catalysis activity.
(3) resulting polymers/titanium dioxide multiple elements design photocatalysis film can use with repetitive cycling, operation Convenient.
Below in conjunction with the accompanying drawings and embodiment the present invention is further illustrated, but it is to be noted following Embodiment is only intended to that the present invention is further illustrated, it is impossible to be not understood as being asked the present invention to protect Protect the restriction of scope.
Accompanying drawing explanation
Fig. 1. the polyvinyl alcohol/titanium dioxide/graphene oxide/silver multiple elements design light of the embodiment of the present invention 1 is urged Change the infrared spectrum of thin film.
Fig. 2. the polyvinyl alcohol/titanium dioxide/graphene oxide/silver multiple elements design light of the embodiment of the present invention 2 is urged Change the transmission electron microscope photo of thin film.
Detailed description of the invention
Embodiment 1
(1) 10ml tetra-n-butyl titanate is joined the trifluoroacetic acid solution that 1.7ml mass concentration is 99% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.03mL concentration in water and after merging is the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, It is placed under uviol lamp irradiation 0.5 hour, is subsequently adding the graphene oxide water that 0.5mL concentration is 0.1g/mL Solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 0.5 hour, take at 180 DEG C Carrying out film on glass after going out cooling, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 0.5 in 180 DEG C Hour, the mass content that i.e. can get titanium dioxide is the polyvinyl alcohol/titanium dioxide/graphite oxide of 66.7% Alkene/silver multiple elements design photocatalysis film.The light transmission test result of product is shown in Table 1;Infrared spectrum such as Fig. 1 Shown in.
Embodiment 2
(1) 10ml tetra-n-butyl titanate is joined in the trifluoroacetic acid solution that 170ml mass concentration is 1% It is hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is stirred vigorously 1 Hour, obtain brown solution, the brown solution obtained directly be dried in air at room temperature, Remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.03mL concentration in water and after merging is the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, It is placed under uviol lamp irradiation 0.5 hour, is subsequently adding the graphene oxide water that 0.5mL concentration is 0.1g/mL Solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 10 hours at 90 DEG C, takes out Carrying out film after cooling on glass, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 5 in 200 DEG C little Time, the mass content that i.e. can get titanium dioxide be the polyvinyl alcohol/titanium dioxide/graphene oxide of 66.7%/ Silver multiple elements design photocatalysis film.The light transmission test result of product is shown in Table 1;Transmission electron microscope photo As shown in Figure 2.
Embodiment 3
(1) 10ml tetraisopropyl titanate is joined the trifluoroacetic acid solution that 38.5ml mass concentration is 99% In be hydrolyzed, wherein tetraisopropyl titanate: the mol ratio of trifluoroacetic acid is 1:10, and room temperature is stirred vigorously 1 hour, obtain brown solution, the brown solution obtained directly be dried in air at room temperature, Remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 5g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in water In and merge after add 0.3mL concentration be the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, is placed in Irradiate 0.5 hour under uviol lamp, be subsequently adding the graphene oxide that 0.001mL concentration is 1g/mL water-soluble Liquid, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 3 hours, take out cold at 160 DEG C But carrying out film after on glass, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 2 in 200 DEG C little Time, the mass content that i.e. can get titanium dioxide be the polyvinyl alcohol/titanium dioxide/graphene oxide of 50%/ Silver multiple elements design photocatalysis film.The light transmission test result of product is shown in Table 1.
Embodiment 4
(1) join in the acetic acid solution that 21.3ml mass concentration is 80% by 10ml tetra-n-butyl titanate Row hydrolysis, wherein tetra-n-butyl titanate: the mol ratio of acetic acid is 1:5, room temperature is stirred vigorously 1 hour, Obtaining brown solution, be directly dried in air at room temperature by the brown solution obtained, removing can Volatile byproducts, obtains titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.03mL concentration in water and after merging is the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, It is placed under uviol lamp irradiation 0.5 hour, is subsequently adding the graphene oxide that 0.01mL concentration is 0.5g/mL Aqueous solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 3 hours, take at 90 DEG C Carrying out film on glass after going out cooling, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 2 in 190 DEG C little Time, the mass content that i.e. can get titanium dioxide be the polyvinyl alcohol/titanium dioxide/graphene oxide of 66.7%/ Silver multiple elements design photocatalysis film.The light transmission test result of product is shown in Table 1.
Embodiment 5
(1) 10ml tetra-n-butyl titanate is joined the trifluoroacetic acid solution that 3.4ml mass concentration is 50% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 2.5g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.01mL concentration in water and after merging is the AgNO of 1mol/L3Aqueous solution, after mix homogeneously, puts Irradiate 0.5 hour under uviol lamp, be subsequently adding the graphene oxide that 0.5mL concentration is 0.1g/mL water-soluble Liquid, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 3 hours, take out cold at 180 DEG C But carrying out film after on glass, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 2 in 180 DEG C little Time, the mass content that i.e. can get titanium dioxide be the polyvinyl alcohol/titanium dioxide/graphene oxide of 66.7%/ Silver multiple elements design photocatalysis film.The light transmission test result of product is shown in Table 1.
Embodiment 6
(1) 10ml tetra-n-butyl titanate is joined the trifluoroacetic acid solution that 3.4ml mass concentration is 50% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 2.5g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.01mL concentration in water and after merging is the AgNO of 1mol/L3Aqueous solution, after mix homogeneously, puts Irradiate 0.5 hour under uviol lamp, be subsequently adding the graphene oxide that 0.5mL concentration is 0.1g/mL water-soluble Liquid, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 3 hours, take out cold at 180 DEG C But carrying out film after on glass, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 2 in 180 DEG C little Time, the mass content that i.e. can get titanium dioxide be the polyvinyl alcohol/titanium dioxide/graphene oxide of 66.7%/ Silver multiple elements design photocatalysis film.
Embodiment 7
(1) 10ml tetra-n-butyl titanate is joined the solution of trichloroacetic acid that 3.4ml mass concentration is 50% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.03mL concentration in water and after merging is the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, It is placed under uviol lamp irradiation 0.5 hour, is subsequently adding the graphene oxide water that 0.5mL concentration is 0.1g/mL Solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 1 hour at 180 DEG C, takes out Carrying out film after cooling on glass, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 2 in 180 DEG C little Time, the mass content that i.e. can get titanium dioxide be the polyvinyl alcohol/titanium dioxide/graphene oxide of 66.7%/ Silver multiple elements design photocatalysis film.
Embodiment 8
(1) 10ml tetra-n-butyl titanate is joined the trifluoroacetic acid solution that 3.4ml mass concentration is 50% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinyl alcohol of 0.5g step (1) obtained is dissolved separately in Adding 0.03mL concentration in water and after merging is the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, It is placed under uviol lamp irradiation 0.5 hour, is subsequently adding the graphene oxide water that 0.5mL concentration is 0.1g/mL Solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 0.5 hour, take at 180 DEG C Carrying out film on glass after going out cooling, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 0.5 in 180 DEG C Hour, the mass content that i.e. can get titanium dioxide is the polyvinyl alcohol/titanium dioxide/graphite oxide of 66.7% Alkene/silver multiple elements design photocatalysis film.
Embodiment 9
(1) 10ml tetra-n-butyl titanate is joined the trifluoroacetic acid solution that 3.4ml mass concentration is 50% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyacrylic acid of 0.5g step (1) obtained is dissolved separately in Adding 0.03mL concentration in water and after merging is the AgNO of 0.1mol/L3Aqueous solution, after mix homogeneously, It is placed under uviol lamp irradiation 0.5 hour, is subsequently adding the graphene oxide water that 0.5mL concentration is 0.1g/mL Solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 0.5 hour, take at 180 DEG C Carrying out film on glass after going out cooling, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 0.5 in 180 DEG C Hour, the mass content that i.e. can get titanium dioxide is the polyacrylic acid/titanium dioxide/graphite oxide of 66.7% Alkene/silver multiple elements design photocatalysis film.
Embodiment 10
(1) 10ml tetra-n-butyl titanate is joined the trifluoroacetic acid solution that 3.4ml mass concentration is 50% In be hydrolyzed, wherein tetra-n-butyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is acutely stirred Mix 1 hour, obtain brown solution, the brown solution obtained directly is done in air at room temperature Dry, remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinylpyrrolidone of 0.5g step (1) obtained is distinguished Adding 0.03mL concentration after being dissolved in the water and merging is the AgNO of 0.1mol/L3Aqueous solution, mixing is all After even, it be placed under uviol lamp irradiation 0.5 hour, be subsequently adding the oxidation stone that 0.5mL concentration is 0.1g/mL Ink aqueous solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 0.5 little at 180 DEG C Time, on glass, carrying out film after taking out cooling, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 0.5 in 180 DEG C Hour, the mass content that i.e. can get titanium dioxide is the polyvinylpyrrolidone/titanium dioxide/oxygen of 66.7% Functionalized graphene/silver multiple elements design photocatalysis film.
Embodiment 11
(1) 10ml tetraethyl titanate is joined in the trifluoroacetic acid solution that 3.4ml mass concentration is 50% It is hydrolyzed, wherein tetraethyl titanate: the mol ratio of trifluoroacetic acid is 1:0.5, and room temperature is stirred vigorously 1 Hour, obtain brown solution, the brown solution obtained directly be dried in air at room temperature, Remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and the 0.25g polyvinylpyrrolidone of 0.5g step (1) obtained is distinguished Adding 0.03mL concentration after being dissolved in the water and merging is the AgNO of 0.1mol/L3Aqueous solution, mixing is all After even, it be placed under uviol lamp irradiation 0.5 hour, be subsequently adding the oxidation stone that 0.5mL concentration is 0.1g/mL Ink aqueous solution, mix homogeneously is placed in autoclave, carries out hydrothermal treatment consists 0.5 little at 180 DEG C Time, on glass, carrying out film after taking out cooling, drying at room temperature obtains high transparency thin film;
(3) high transparency thin film step (2) obtained under vacuum, carries out heat treatment 0.5 in 180 DEG C Hour, the mass content that i.e. can get titanium dioxide is the polyvinylpyrrolidone/titanium dioxide/oxygen of 66.7% Functionalized graphene/silver multiple elements design photocatalysis film.
Comparative example 1
Experiment condition, substantially with embodiment 1, is a difference in that and carries out heat treatment 2.5 hours at 200 DEG C.Produce The light transmission test result of product is shown in Table 1.
Comparative example 2
Experiment condition, substantially with embodiment 1, is a difference in that and carries out heat treatment 10 minutes at 200 DEG C.Produce The light transmission test result of product is shown in Table 1.
Table 1.
Embodiment Light transmittance/%
Embodiment 1 95
Embodiment 2 94
Embodiment 3 96
Embodiment 4 93
Embodiment 5 95
Comparative example 1 85
Comparative example 2 90
Thin film light transmittance is carried out according to GB GB/T 2410-2008 " transparent plastic light transmittance and the mensuration of mist degree " Test.

Claims (6)

1. a preparation method for polymer/titanium dioxide multiple elements design photocatalysis film, is characterized in that, institute The preparation method stated comprises the following steps:
(1) titanate esters is joined in organic acid soln it is hydrolyzed, wherein: titanate esters: rubbing of organic acid That ratio is 1:0.5~10;It is stirred at room temperature, the solution obtained directly is dried in air at room temperature, removes Remove volatile by-product, obtain titanium dioxide xerogel;
(2) titanium dioxide xerogel and water-soluble polymer step (1) obtained is dissolved in water also Silver nitrate aqueous solution is added, wherein: titanium dioxide xerogel: water-soluble polymer: silver nitrate after merging Mass ratio be 1:(0.5~10): (0.001~0.01);After mix homogeneously, it is placed under uviol lamp irradiation 0.5~3 After hour, adding graphene oxide water solution, wherein graphene oxide is 1 with the mass ratio of titanium dioxide: 10~500;Being subsequently placed in autoclave and carry out hydrothermal treatment consists, wherein, the temperature of hydrothermal treatment consists is 90~180 DEG C;The time of hydrothermal treatment consists is 0.5~10 hour;Molten by obtain after hydrothermal treatment cooling Liquid carries out film on solid substrate, and drying at room temperature obtains transparent membrane;
(3) transparent membrane that step (2) obtains is carried out heat treatment under vacuum, obtain polymer/bis- Titanium oxide multiple elements design photocatalysis film, wherein, the described temperature carrying out heat treatment under vacuum It it is 180~200 DEG C;The time of heat treatment is 0.5~5 hour;
Described polymer one in polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone.
Preparation method the most according to claim 1, is characterized in that: described titanate esters is selected from metatitanic acid four One or more in ethyl ester, tetraisopropyl titanate, tetra-n-butyl titanate.
Preparation method the most according to claim 1, is characterized in that: the quality of described organic acid soln Concentration is 1%~99%.
4. according to the preparation method described in claim 1 or 3, it is characterized in that: described organic acid is selected from second One in acid, trifluoroacetic acid, trichloroacetic acid.
Preparation method the most according to claim 1, is characterized in that: described silver nitrate aqueous solution dense Degree is 0.1~1mol/L.
Preparation method the most according to claim 1, is characterized in that: described graphene oxide water solution Concentration be 0.1~1g/mL.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102631949A (en) * 2011-02-12 2012-08-15 首都师范大学 Modified visible-light responsive titania doped photocatalyst and production method and uses thereof
CN102688755A (en) * 2011-12-12 2012-09-26 湖南理工学院 Ag/TiO2/graphene nanometer composite photocatalyst and preparation method thereof
CN103144388A (en) * 2013-03-21 2013-06-12 四川农业大学 Preparation method and application of polyaniline/titanium dioxide/graphene conductive composite membrane

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130224452A1 (en) * 2012-02-28 2013-08-29 Indian Institute Of Technology Madras Metal nanoparticle-graphene composites and methods for their preparation and use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102631949A (en) * 2011-02-12 2012-08-15 首都师范大学 Modified visible-light responsive titania doped photocatalyst and production method and uses thereof
CN102688755A (en) * 2011-12-12 2012-09-26 湖南理工学院 Ag/TiO2/graphene nanometer composite photocatalyst and preparation method thereof
CN103144388A (en) * 2013-03-21 2013-06-12 四川农业大学 Preparation method and application of polyaniline/titanium dioxide/graphene conductive composite membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Xiangfu Meng等.Preparation of Polyacrylic Acid/TiO2 Nanocomposites and Its Application in Photodegradation of Methyl Orange.《Materials Science Forum》.2011,第694卷第234-238. *

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